Phenyl-mercaptomethane-sulfonamide



United States Patent 1 Claim. (Cl: 260-556) ABSTRACT OF THE DISCLOSUREPhenyl-mercaptomethane-sulfonamide which possesses fungicidal propertiesand which may be produced by conventional methods.

The present invention relates to henyl-mercaptomethane-sulfonamide,which has fungitoxic properties, to compositions thereof withdispersible carrier vehicles, as well as to the preparation and usethereof.

It is already known that zinc propylene-bis-dithio-carbamate (A), zincethylene-bis-dithio-carbamate (B) andN-(trichloromethyl-thio)-tetrahydro-phthalimide (C) can be used withgood results for combating parasitic fungi on parts of plants aboveground, such as species of Phytophthora, Peronospora and Venturia.

It is an object of the present invention to provide the particular newcompound phenyl-mercaptomethane-sulfonamide, which possesses valuablefungitoxic properties; to provide active compositions thereof in theform of mixtures with solid and liquid dispersible carrier vehicles; toprovide a process for producing such compound, and to provide methods ofusing such compound in a new way, especially for combating fungi and, inparticular, parasitic fungi.

Other and further objects of the present invention will become apparentfrom a study of the within specification and accompanying examples.

It has now been found that the particular new compoundphenyl-mercaptomethane-sulfonamide, which has the formula:

sonis 02-NHZ has strong fungitoxic properties.

It has been further found that such new compoundphenyl-mercaptomethane-sulfonamide is obtained by the process whichcomprises reacting thiophenol, in the presence of an acid-binding agent,with a halomethane-sulfonamide of the general formula:

Q-sn oi-oni-somni NaOH Q-s-orn-somm 3,412,149 Patented Nov. 19, 1968"ice The two starting materials required for the above reaction areknown. Such reaction is preferably carried out in the presence of water.However, it is also possible to use aqueous solutions of water-solubleorganic solvents, such as alcohols, ketones and dimethyl formamide.

All conventional acid-binding agents can be used as acid binders herein,especially those which are water-soluble. Alkali metal hydroxides, suchas potassium hydroxide and sodium hydroxide, and alkali metalcarbonates, such as potassium carbonate and sodium carbonate, areparticularly suitable.

The reaction temperatures for the production process herein may bevaried within a fairly wide range. In general, the operation is carriedout substantially between about 50 and 120 C., preferably between 60 andC. The boiling temperature of the aqueous reaction mixture is especiallysuitable when working at atmospheric pressure.

To carry out the instant process, the starting materials and theacid-binding agent are expediently used in a molar ratio of 1:1:1. It ispossible to go above or remain below these proportions by a deviation ofup to about 20%, Without substantially reducing the yield.

The instant reaction is carried out in the usual manner. For example,the thiophenol can be mixed first with an aqueous solution of theacid-binding agent and the chloromethane-sulfona-mide subsequentlyintroduced into this mixture. The reaction mixture is expediently heatedat boiling temperature for some time. The final product crystallizes outupon cooling.

Phenyl mercaptomethane sulfonamide has a strong fungicidal activity. Dueto its advantageously low toxicity towards warm-blooded creatures, it issuitable for combating undesirable plant growth. The good compatibilityof tlie instant compound with higher plants enables such compound to beused eifectively as plant protective agent against fungus plantdiseases, especially in crop control endeavors, without damage to thedesired higher plants.

The instant compound has a particularly good, i.e. ef fective,fungicidal activity against parasitic fungi on plant parts above ground,such as species of Phytophthora, Peronospora and Venturia.

It must be especially emphasized that the instant active compound hasnot only a protective action but also a curative effect, i.e., thefungicidal action is evident even when applied after contamination withthe spores of the fungus. Attention should also 'be drawn to thesystemic action of the instant compound.

Thus, it is possible in accordance with the present invention to protectplants against infestation with fungi by supplying the plant parts aboveground with the instant active compound via the soil and the roots,i.e., systemically. The protective (preventive), as well as curative andsystemic activity of the instant compound against fungi, of course, maybe achieved without causing any damage to higher plants, whereby theinstant compound may be used without restriction in crop controlpursuits.

Thus, the new compound of the instant invention can be used as afungicide, especially for combating parasitic fungi, either alone or inadmixture with solid or liquid carriers or diluents.

The active compound according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withdispersible carrier vehicles, such as solutions, emulsions, suspensions,emulsifiable concentrates, spray powders, pastes, soluble powders,dusting agents, granulates, etc. These are prepared in known manner, forinstance by extending the active agent with dispersible liquid diluentcarriers and/ or dispersible solid carriers optionally with the use ofcarrier vehicle assistants including emulsifying agents and/ordispersing agents, whereby, for example, in the case where water is usedas diluent, organic solvents may be added as auxiliary solvents (cf.Agricultural Chemicals, March 1960, pages 3538). The following may bechiefly considered for use as carrier vehicles for this purpose:dispersible liquid. diluent carriers, such as aromatic hydrocarbons (forinstance, benzene, toluene, xylene, etc.), halogenated, especiallychlorinated, aromatic hydrocarbons (for instance, chlorobenzenes),parafi'ins (for instance, petroleum fractions), chlorinated aliphatichydrocarbons (for instance, methylene chloride, etc.), alcohols (forinstance, methanol, ethanol, propanol, butanol, etc.), ethers,ether-alcohols (for instance, glycol monomethyl ether, etc.), amines(for instance, ethanolamine, etc.), amides (for instance, dimethylformamide, etc.), ketones (for instance, acetone, etc.), and water; aswell as dispersible finely divided solid carriers, such as naturalground minerals (for instance, kaolins, alumina, silica, chalk, i.e.,calcium carbonate, talc, kieselguhr, etc.) and synthetic ground minerals(for instance, highly dispersed silicic acid, silicates, e.g., alkalisilicates, etc.); whereas the following may 'be chiefly considered foruse as carrier vehicle assistants for this purpose: emulsifying agents,such as nonionic and anionic emulsifying agents (for instance,polyethylene oxide esters of fatty acids, polyethylene oxide ethers offatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especiallyalkyl aryl-polyglycol ethers, magnesium stearate, sodium oleate, etc.);and dispersing agents, such as lignin, sulfite waste liquors, methylcellulose, etc.

As will be appreciated by the artisan, the active compound according tothe instant invention may be present in such formulations orcompositions in the form of mixtures with one or more carrier vehiclestogether and with other known active substances, if desired.

The substance according to the invention may be employed, therefore, byitself as the artisan will appreciate, in the form of its compositionswith solid or liquid dispersible carrier vehicles or other knowncompatible active agents, or in the form of particular dosagepreparations for specific application made therefrom, such as solutions,emulsions, suspensions, powders, pastes, and granulates which are thusready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 0.1 and 95% 'by weight,and preferably 0.5 and 90% by weight, of the mixture, Whereas carriercomposition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.0001 and preferably0.001 and 1%, by weight of the mixture. Thus, the present inventioncontemplates over-all compositions which comprise mixtures of adispersible carrier vehicle such as a dispersible carrier solid, or adispersible carrier liquid preferably including a carrier vehicleassistant such as an emulsifying agent and/or a dispersing agent, and anamount of the active compound which is effective for the purpose inquestion and which is generally between about 0.0001 and 95% by weightof the mixture. Specifically, the active compound may be applied to agiven area of soil, for instance, in concentrations substantiallybetween about 0.1 and 5 kg. per hectare. It will be realized that theconcentration of the active compound in question may vary within afairly wide range and will depend upon the fungus diseases against whichthe plants are to be protected, yet the foregoing ranges are typical forthe usual case.

Furthermore, the present invention contemplates methods of selectivelycontrolling or combating fungi, e.g., parasitic fungi, which compriseapplying to at least one of (a) such f ngi and 0 their habit t, afungicidally Example l.Phytophthora test Parts by weight Solvent(acetone) 4.7 Dispersing agent (alkylaryl polyglycol ether) 0.3 WaterThe amount of the particular active compound required for the desiredconcentration of such active compound in a spray liquor is mixed withthe stated amount of solvent and the resulting concentrate then dilutedwith the stated amount of water containing the dispersing agent.

Young tomato plants (Bonny best) with 2-6 foliage leaves are sprayedwith the subject spray liquor until dripping wet. The plants are kept ina greenhouse for 24 hours at 20 C. and at a relative atmospherichumidity of 70%. The tomato plants are then inoculated with an aqueousspore suspension of Phytophthora infestans. The plants are transferredto a moist chamber with an atmospheric humidity of and a temperature of18-20 C.

After 5 days, the infestation of the tomato plants is determined as apercentage of the untreated, but also inoculated, control plants. 0%indicates that on infestation occurred, whereas 100% indicates that theinfestation is exactly the same as that of the control plants.

The active compounds, their concentrations and the results obtained canbe seen from the following Table 1:

TABLE I.--PHYTOPHTIIORA TEST Infestation in percent 01 infestation ofuntreated control at a concentration of active compound 0i ActiveCompound Example 2.Plasmopa=ra test Parts by weight Solvent (acetone)4.7 Dispersing agent (alkylaryl polyglycol ether) 0.3 Water 95 untildripping wet. The plants are kept in a greenhouse for 24 hours at 20 C.and at a relative atmospheric humidity of 70%. The vines aresubsequently inoculated with an aqueous spore suspension of Plasmoparaviticola. The plants are transferred into a moist chamber with anatmospheric humidity of 100% and a temperature of 20 22 C.

After 5 days, the infestation of the vines is determined as a percentageof the untreated but also inoculated control plants. 0% indicates thatno infestation occurs whereas 100% indicate that the infestation isexactly the same as that of the control plans.

The active compounds, their concentration and the results obtained canbe seen from the following Table 2:

TABLE 2.PLASMOPAEA TEST Infestation in percent of infestation ofuntreated control at a concentration Active Compound of active compoundof- Example 3.Fusicladium test (apple scab)/curative Parts by weightSolvent (acetone) 4.7 Emulsifier (alkylaryl polyglycol ether) 0. Water95 The amount of the particular active compound required for the desiredfinal concentration of such active compound in a spray liquid is mixedwith the stated amount of solvent and the resulting concentrate thendiluted with the stated amount of water which contains the emulsifier.

Young apple seedlings with 4-6 foliage leaves are inoculated with anaqueous conidium suspension of Fusioladium dendriticum which causesapple scab, and incubated for 18 hours in a most chamber at 18-20 C. andat an atmospheric humidity of 100%. The plants are subsequently placedin a greenhouse to dry.

After standing for 24 hours, the plants are sprayed dripping wet withthe subject spray liquid, prepared in the above'manner, and again placedin the greenhouse.

Fifteen days after inoculation, the infestation of the apple seedlingsis determined as a percentage of the untreated but also inoculatedcontrol plants.

of time between inoculation and spraying and the results obtained can beseen from the following Table 3:

TAB LE 3.--F USICLADIUM TEST/CURATIVE Infestation in percent;

The amount of the particular active compound required for the desiredfinal concentration of such active compound in a spray liquid is mixedwith the stated amount of solvent and the resulting concentrate thendiluted with the stated amount of water containing the emulsifier.

The terminal feathers of the feathery leaves of young tomato plants(Bonny best) with 2-6 foliage leaves are separated and placed into moistPetri dishes. In these dishes, the leaves are inoculated with an aqueoussuspension of zoosporangia of Phytophthora infestans. The terminalfeathers remain in the closed dishes for a definite period of time.

After this residence time, the inoculated leaves are dipped into thepreparation of the subject active compound and the excess amount ofliquid is wiped oif. The leaves are returned to the Petri dishes andincubated in a climatic cabinet at 20 C. for 72 hours.

The infestation of the leaves is then determined as a percentage of theuntreated but also inoculated control leaves. 0% indicates that noinfestation occurred, whereas 100% indicates that the infestation isexactly the same as that of the control leaves.

The active compounds, their concentrations, the residence time and theresults obtained can be seen from the following Table 4:

TABLE 4.PHYTOPHTHORA TEST/CURATIVE Infestation in percent of infestationof untreated control Resi- Aetive Compound rtlenco at a concentration ofactive compound of line, hours 0.2% 0.1% 0.05% 0.025% 0. 012.5%CHzNH-C-S Z 6 100 (B) n is 100 CHrNH(|;,-S

(known) s0 NH2 6 u 18 32 (I) Q S CH2 16 s3 0% indicates that noinfestation occurred, whereas 100% indicates that the infestation isexactly the same as that of the control plants.

Example 5.-Phytophthora test/ systemic Parts by weight Solvent (acetone)4.7 Emulsifier (alkylaryl polyglycol ether) 0.3

The active compounds, their concentrations, the period 75 Water 7 8 Theamount of the given active compound required for The active compounds,their concentration and the rethe desired final concentration of suchactive compound sults obtained can be seen from the following Table 6:

TABLE 6.PHYTOPHTHORA TEXT/FIELD TEST (A) Zincpropylene-bisdithio-carbarnate 1.0 65.3

1 SC1I SOzNH o.

(A) Zinc propylene-bis-dithio-carbarnate.-- 0. 5

in a spray liquid is mixed with the stated amount of sol- The followingexample is given for the purpose of vent and the resulting concentratethen diluted with the illustrating, while not limiting, the productionprocess stated amount of water containing the emulsifier. in accordancewith the present invention:

Young tomato plants (Bonny best) with 3-5 foliage leaves, which havebeen potted in standard soil, are drenched with the subject spray liquidthree times at intervals of 24 hours so that only the soil at the bottomS OHPSO2 NH2 of the pot is completely soaked. 24 hours after the lasttreatment, the plants are inoculated with an aqueous suspension ofzoosporangia of the fungus Phytophthora infarms The plants aretransferred into a moist chamber 25 Witch a stirrer. 1.5 liters of water(preferred temperature with an atmospheric humidity of 100% and atempera- 60 of a by volume Sodlum tum droxlde solutlon are subsequentlyadded and then 260 g.

After 5 days, the infestation of the tomato plants is (2 11101). ofchlorohtethahe'u1fham1de determined as a percentage f untreated, butalso C.) are introduced, with stirring. The reactton mixture isinoculated control plants. 0% indicates that no infesta- 3O heated tohoihhg and p at boiling for one The Example 7 220 grams (2 mol) ofthiophenol (B.P. 6668 C./l3 mm. Hg) are placed in a flask of 4 literscapacity equipped tion occurred, whereas 100% indicates that theinfestaaction mixture is then allowed to 6001, While Stirring tion isexactly the same as that of the control plants. is Continued, whereuponthe crhdfi Product Separates in The subject active compound, itsconcentrations, a d crystalline form. The product is dried on unglazedplates the results obtained can be seen from the following or metalsheets under a hood at room temperature and Table 5-' 35 recrystallizedfrom benzene (+10% by volume alco- IABLE 5.-PHYTOPHTHORA TEST/SYSTEMICInfestation in percent of infestation of untreated control at aconcentration of active compound Active Compound ofhol)/petroleum ether.There are obtained 200 to 210 g.

Example 6.-Phytophthora test/field test of a colorless, slightlyflocculent product, i.e. phenylmereaptomethane-sulfonamide; M.P. l01103C. Yield In open land, three test lots per active compound (3 of pureproduct: to 52% of theory.

repeats) with potatoes of the Grata variety were sprayed It will beappreciated that the instant specification and on four dates (July 7,July 16, Aug. 4 and Aug. 21) with 50 examples are set forth by way ofillustration and not spray liquids prepared from the given activecompound. limitation, and that various modifications and changes Thespray liquids were prepared from wettable powders y he made Withoutdeparting from the Spirit and SCOPE with a content of 70% activecompound by diluting with of the Present invention which is to belimited y y water. 1000 liters spray liquor per hectare were used in theshop? of h plf i each case, 55 What IS clalmed 1s:

The natural infestation with Phytophthora infestansphenyl'mercapto'methane'sulfonamide having the occurred only very latein the plant season, so that mainly formula the last spray treatmentbecame effective.

Evaluation took place eon the 26th of Aug. following S GIL-S OPNH, thlast above data by counting in every test lot the References Citedinfested and the healthy feathery leaves of 10 shoots with about 15-20feathery leaves. The infestation of the leaves UNITED STATES PATENTStaken from the treated lots was expressed as a percentage 3,086,974 4/1963 Schlorz et al. 260-556 X of the infestation of the leaves takenfrom the untreated control lot, i.e., the infestation of the control lotwas HENRY R'JILESPrmary Exammerset at 100. H. I. MOATZ, AssistantExaminer.

